The present invention relates to novel herbicidally active 3-hydroxy-4-aryl-5-oxopyrazoline derivatives, to processes for their preparation, to compositions which comprise these compounds and may additionally comprise safeners, and to the use of these compounds as herbicides for controlling weeds and grasses, in particular in crops of useful plants.
3-Hydroxy-4-aryl-5-oxopyrazoline derivates having herbicidal action are described, for example, in EP-A-0 508 126, WO 96/25395 and WO 96/21652. We have now found novel 3-hydroxy-4-aryl-5-oxopyrazoline derivatives having herbicidal properties.
The present invention thus provides compounds of the formula I 
in which
R1, R2 and R3 independently of one another are halogen, nitro, cyano, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkyl, C2-C6haloalkenyl, C3-C6cycloalkyl, halogen-substituted C3-C6cycloalkyl, C1-C6alkoxyalkyl, C1-C6alkylthioalkyl, hydroxyl, mercapto, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkylamino or di(C1-C4-alkyl)amino;
R4 and R5 together are a group
xe2x80x94Cxe2x80x94R6(R7)xe2x80x94Oxe2x80x94Cxe2x80x94R8(R9)xe2x80x94Cxe2x80x94R10(R11)xe2x80x94Cxe2x80x94R12(R13)xe2x80x94xe2x80x83xe2x80x83(Z1),
xe2x80x94Cxe2x80x94R14(R15)xe2x80x94Cxe2x80x94R16(R17)xe2x80x94Oxe2x80x94Cxe2x80x94R18(R19)xe2x80x94Cxe2x80x94R20(R21)xe2x80x94xe2x80x83xe2x80x83(Z2),
or
xe2x80x94Cxe2x80x94R22(R23)xe2x80x94Cxe2x80x94R24(R25)xe2x80x94Cxe2x80x94R26(R27)xe2x80x94Oxe2x80x94Cxe2x80x94R28(R29)xe2x80x94xe2x80x83xe2x80x83(Z3);
in which
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, and R29 independently of one another are hydrogen, halogen, C1-C4alkyl or C1-C4haloalkyl where an alkylene ring, which together with the carbon atoms of the groups Z1, Z2 or Z3 contains 2 to 6 carbon atoms and may be interrupted by oxygen, may either be fused or spiro-linked to the carbon atoms of the groups Z1, Z2 or Z3, or where this alkylene ring bridges at least one ring atom of the groups Z1, Z2 or Z3;
G is hydrogen, xe2x80x94C(X1)xe2x80x94R30, xe2x80x94C(X2)xe2x80x94X3xe2x80x94R31, xe2x80x94C(X4)xe2x80x94N(R32)xe2x80x94R33, xe2x80x94SO2xe2x80x94R34, an alkali metal, alkaline earth metal, sulfonium or ammonium cation or xe2x80x94P(X5)(R35)xe2x80x94R36;
X1, X2, X3, X4 and X5 independently of one another are oxygen or sulfur; and
R30, R31, R32, R33, R34, R35 and R36 independently of one another are hydrogen, C1-C5alkyl, C1-C5haloalkyl, C2-C5alkenyl, C1-C5alkoxyalkyl, C3-C6cycloalkyl or phenyl, and R34 is additionally C2-C20alkenyl, C2-C20alkenyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosultonyl, alkylsultonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkyl-alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or substituted heteroaryl, C2-C20alkynyl, C2-C20alkynyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkyiamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkyl-alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or substituted heteroaryl, (C1-C7)cycloalkyl, (C1-C7)cycloalkyl substituted by halogen, haloalkyl, (C1-C6)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or trialkylsilyloxy, heteroaryl, heteroaryl substituted by halogen, haloalkyt, nitro, cyano, (C1-C6)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or trialkylsilyloxy, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloalkylamino, substituted cycloalkylamino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, and salts and diastereomers of the compounds of the formula I.
In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. The alkyl groups in the definitions of the substituents are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, and the isomeric pentyls and hexyls. Suitable cycloalkyl substituents contain 3 to 6 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. These may be mono- or polysubstituted by halogen, preferably by fluorine, chlorine or bromine. Alkenyl is to be understood as meaning, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethinyl, propargyl, but-2-in-1-yl, 2-methylbutin-2-yl or but-3-in-2-yl. Haloalkyl groups preferably have a chain length of 1 to 4 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl. Suitable haloalkenyls are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among the C2-C6alkenyl groups which are mono-, di- or trisubstituted by halogen, preference is given to those having a chain length of 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, and the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Alkylthio groups preferably have a chain length of 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Alkoxyalkyl groups preferably have 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.
Phenyl may be substituted. In this case, the substituents may be in the ortho, meta and/or para position. The substituents are preferably located in the positions ortho and para to the site where the ring is attached.
The halogen, alkyl, cycloalkyl, alkoxy, alkylthio, alkylcarbonyl, alkylsulfonyl and (di)alkylamino radicals which may be present in the radicals R34, in particular xe2x80x94SO2R34 (G), are derived from the corresponding radicals mentioned above. Preferred heterocyclyl radicals are those containing 1 or 2 heteroatoms, for example N, S or O. They are usually saturated. Heteroaryl radicals are customarily aromatic heterocycles which preferably contain 1 to 3 heteroatoms, such as N, S and O. Examples of suitable heterocycles and heteroaromatics are: pyrrolidine, piperidine, pyran, dioxane, azetidine, oxetan, pyridine, pyrimidine, triazine, thiazole, thiadiazole, imidazole, oxazole, isoxazole and pyrazine, furan, morpholine, piperazine, pyrazole, benzoxazole, benzothiazole, quinoxaline and quinoline. These heterocycles and heteroaromatics may also be substituted, for example by halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, thioalkyl, alkylamino or phenyl. The C2-C20alkenyl and alkynyl groups R34 may be mono- or polyunsaturated They preferably contain 2 to 12, in particular 2 to 6, carbon atoms. For illustration, suitable groups xe2x80x94SO2R34 are given in the example below: 
Alkali metal cations, alkaline earth metal cations or ammonium cations for the substituent G are, for example, the cations of sodium, potassium, magnesium, calcium and ammonium. Preferred sulfonium cations are, in particular, trialkylsulfonium cations, where the alkyl radicals each preferably contain 1 to 4 carbon atoms.
The free valency on the left hand of the groups Z1, Z2 and Z3 is linked to the 1-position and the free valency on the right hand is linked to the 2-position of the pyrazoline ring.
Compounds of the formula I, in which an alkylene ring which, together with the carbon atoms of the groups Z1, Z2 and Z3 contains 2 to 6 carbon atoms may be fused or spiro-linked to the groups Z1, Z2 and Z3, have, for example, the following structure: 
Compounds of the formula I, in which in the groups Z1, Z2 or Z3 an alkylene ring bridges at least one ring atom of the groups Z1, Z2 or Z3, have, for example, the following structure: 
R4 and R5 together are in particular a group
xe2x80x94Cxe2x80x94R6(R7)xe2x80x94Oxe2x80x94Cxe2x80x94R8(R9)xe2x80x94Cxe2x80x94R10(R11)xe2x80x94Cxe2x80x94R12(R13)xe2x80x94xe2x80x83xe2x80x83(Z1),
xe2x80x94Cxe2x80x94R14(R15)xe2x80x94Cxe2x80x94R16(R17)xe2x80x94Oxe2x80x94Cxe2x80x94R18(R19)xe2x80x94Cxe2x80x94R20(R21)xe2x80x94xe2x80x83xe2x80x83(Z2),
or
xe2x80x94Cxe2x80x94R22(R23)xe2x80x94Cxe2x80x94R24(R25)xe2x80x94Cxe2x80x94R26(R27)xe2x80x94Oxe2x80x94Cxe2x80x94R28(R29)xe2x80x94xe2x80x83xe2x80x83(Z3);
in which
R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28 and R29 independently of one another are hydrogen, halogen, C1-C4alkyl or C1-C4haloalkyl, where an alkylene ring which, together with the carbon atoms of the groups Z1, Z2 and Z3, contains 3 to 6 carbon atoms may be fused or spiro-linked to the groups Z1, Z2 and Z3.
Among the compounds of the formula I, preference is given to those in which G is hydrogen. In a particularly preferred group of compounds of the formula I, R4 and R5 together form a group Z2. Also of particular interest are compounds of the formula I in which R1, R2 and R3 independently of one another are halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl or C1-C6-alkoxy. Particular preference is given to compounds of the formula I in which R2 is halogen, methyl, ethyl or ethinyl, and to compounds of the formula I in which R1 and R3 independently of one another are methyl, ethyl, isopropyl, vinyl, allyl, ethinyl, methoxy, ethoxy, bromine or chlorine. Very particular preference is given to compounds of the formula I in which G is the group xe2x80x94C(X1)xe2x80x94R30 or C(X2)xe2x80x94(X3)xe2x80x94R31 in which X1, X2 and X3 are, in particular, oxygen, and R30 and R31 independently of one another are preferably C1-C5alkyl. Preference is furthermore given to compounds of the formula I in which R30, R31, R32, R33, R34, R35 and R36 independently of one another are hydrogen, C1-C5alkyl or C1-C5haloalkyl.
Another preferred group of compounds of the formula I is is that where at least one ring atom of the groups Z1, Z2 or Z3 is bridged by an alkylene ring which, together with the carbon atoms of the groups Z1, Z2 or Z3, contains 2 to 6 carbon atoms and may be interrupted by oxygen.
The invention also includes the salts which the compounds of the formula I can form with acids. Suitable acids for forming the acid addition salts are both organic and inorganic acids. Examples of such acids are hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid. The salts of the compounds of the formula I with acidic hydrogen also include alkali metal salts, for example sodium salts and potassium salts; alkaline earth metal salts, for example calcium salts and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or polysubstituted ammonium salts, and salts with other organic nitrogen bases. Correspondingly, suitable salt formers are alkali metal and alkaline earth metal hydroxides, in particular the hydroxides of lithium, sodium, potassium, magnesium or calcium, where those of sodium or potassium are particularly important.
Examples of amines which are suitable for forming ammonium salts are both ammonia and primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methyinonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o, m, p-toluidines, phenylenediamines, benzidines, naphthylamines and o, m, p-chloroanilines; but in particular triethylamine, isopropylamine and diisopropylamine.
In the processes described in this application, unless chiral starting materials are employed, the unsymmetrically substituted compounds of the formula I are generally obtained as racemates. The stereoisomers can then be separated by known methods, such as fractional crystallization after salt formation with optically pure bases, acids or metal complexes, or else by chromatographic processes such as high pressure liquid chromatography (HPLC) on acetylcellulose, owing to their physicochemical properties. In the present invention, the active compounds of the formula I are to be understood as meaning both the enriched and optically pure forms of the stereoisomers in question, and the racemates or diastereomers. Unless specific reference is made to the individual optical isomers, the given formula is to be understood as meaning those racemic mixtures which are formed in the preparation process mentioned. If an aliphatic Cxe2x95x90C double bond is present, geometrical isomerism may additionally occur.
Also depending on the type of the substituents, the compounds of the formula I may be present as geometrical and/or optical isomers and isomer mixtures, and also as tautomers and mixtures of tautomers. These compounds of the formula I likewise form part of the subject-matter of the present invention. The compounds of the formula I in which the group G is hydrogen may, for example, be present in the following tautomer equilibriums: 
If G is different from hydrogen and Z is the group Z1 or Z3, or if G is different from hydrogen and Z2 is unsymmetrically substituted, fused or spiro-linked, the compound of the formula I may be present as an isomer of the formula Id 
Processes for preparing compounds which, with respect to the meaning of the substituents R4 and R5, are different from the compounds of the formula I according to the present invention are, for example, described in WO 96/21652. The compounds of the formula I according to the present invention can be prepared by methods similar to the processes described in WO 96/21652. The compounds of the formula II 
in which R1, R2, R3, R4 and R5 are as defined under formula I and which are employed as starting materials for such processes can be prepared, for example, by reacting a compound of the formula III 
in which R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl, and R1, R2 and R3 are as defined under formula I in an inert organic solvent, if appropriate in the presence of a base, with a compound of the formula IV or IVa 
in which R4 and R5 are as defined under formula I. Other preparation processes for compounds of the formula II are described, for example, in WO 92/16510.
The compounds of the formula III are either known, or they can be prepared similarly to known processes. Processes for preparing compounds of the formula III and their reaction with hydrazines are described, for example, in WO 97/02243. Compounds of the formula III in which R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl, and R1, R2 and R3 are as defined under formula I can be prepared by methods known to the person skilled in the art. For example, compounds of the formula III in which R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl, and R1, R2 and R3 independently of one another are C1-C4alkyl, C2C4alkenyl, C2-C4alkynyl can be prepared by the process of cross-coupling according to Stille (J. K. Stifle, Angew. Chem. 1986, 98, 504-519), Sonogashira (K. Sonogashira et al., Tetrahedron Lett. 1975, 4467-4470), Suzuki (N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483) or Heck (R. F. Heck, Org. React. 1982, 27, 345-390), with or without subsequent hydrogenation. This procedure is illustrated by the following reaction scheme: 
The compounds of the formulae IV and IVa are either known, or they can be prepared by known processes. Processes for preparing compounds of the formula IV are described, for example, in WO 95/00521. These compounds can be prepared, for example, by heating a compound of the formula V 
in which R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy, benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy and R4 and R5 are as defined under formula I in the presence of a base or an acid in an inert solvent. Compounds of the formula V in which R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy, benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy and R4 and R5 are as defined under formula I can be prepared, for example, by reacting a compound of the formula VI 
in which R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy, benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichforoethoxy, tert-butoxy or benzyloxy in the presence of a base and an inert solvent with a compound of the formula VII
Y"Brketopenst"Z1, Z2, or Z3"Brketclosest"Yxe2x80x83xe2x80x83(VII),
in which Y is halogen, alkyllaryl sulfonates xe2x80x94OSO2R43, preferably bromine, chlorine, iodine, mesylate (R43=CH3), triflate (R43=CF3) or tosylate (R43=p-tolyl) and Z1, Z2, and Z3 are defined under formula I. In the formula VII, the free valencies of the groups Z1, Z2and Z3 are in each case attached to the group Y. Compounds of the formula VI and VII are known, or they can be prepared by methods known to the person skilled in the art.
Compounds of the formula IV in which R4 and R5 together are a group Z2 xe2x80x94Cxe2x80x94R14(R15)xe2x80x94Cxe2x80x94R16(R17)xe2x80x94Oxe2x80x94Cxe2x80x94R18(R19)xe2x80x94Cxe2x80x94R20(R21)xe2x80x94 (Z2), in which R14, R15, R16, R17, R18, R19, R20 and R21 are hydrogen can be prepared, for example, according to the following reaction scheme: 
Compounds of the formula I in which R4 and R5 are a group Z1 or Z3 can be prepared using the methods of the synthesis examples given above. Thus, the compounds of the formula III can, for example, be reacted with a hydrazine alkanol of the formula IV(b) 
(here, R6-R13 and R22-R29 are hydrogen) to give the compounds of the formula IVc 
followed by a cyclization, for example with formaldehyde, to give the end products of the formula Ie 
The compound of the formula Ie in which R1 and R3 are ethyl and R2 is methyl has a melting point of 186-191xc2x0 C. (decomp.). Similarly, it is also possible to prepare compounds of the formula I in which the substituents R6-R13 and R2-R29 are different from hydrogen and, independently of one another, have one of the meanings mentioned for them above.
The end products of the formula I can be isolated in a customary manner by concentration and/or evaporation of the solvent and be purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, alkanes, aromatic hydrocarbons or chlorinated hydrocarbons, or by chromatography. Salts of compounds of the formula I can be prepared in a manner known per se. Such preparation methods are described, for example, in WO 96/21652.
The compounds of the formula I or compositions comprising them can be used according to the invention by all the application methods customary in agriculture, for example pre-emergence application, postemergence application and seed dressing, and various methods and techniques, for example controlled release of active compounds. To this end, the active compound is absorbed in solution onto mineral granule carriers or polymerized granules (urea/formaldehyde) and dried. If appropriate, a coating which allows the active compound to be released in metered form over a certain period of time can additionally be applied (coated granules).
The compounds of the formula I can be employed as herbicides in unchanged form, i.e. as they are obtained in the synthesis, but they are preferably processed in a customary manner with the auxiliaries conventionally used in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The methods of application, such as spraying, atomizing, dusting, wetting, scattering or watering, in the same way as the nature of the compositions, are chosen according to the required aims and the given circumstances.
The formulations, i.e. the compositions, formulations or preparations comprising the active compound of the formula I or at least one active compound of the formula I and as a rule one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with the formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) can furthermore additionally be used during the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485 on page 6. Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, nonionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8.
The surfactants conventionally used in the art of formulation and which can also be used to prepare the herbicidal compositions according to the invention are described, inter alia, in xe2x80x9cMc Cutcheon""s Detergents and Emulsifiers Annualxe2x80x9d, MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol I-III, Chemical Publishing Co., New York, 1980-81.
The efficacy of herbicidal and plant-growth-inhibiting compositions according to the invention containing a herbicidally effective amount of a compound of the formula I can be enhanced by addition of spray tank adjuvants.
These adjuvants may be, for example: nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with and without surfactants, vegetable oil derivatives with and without addition of surfactants, alkylated derivatives of oils of vegetable or mineral origin with and without surfactants, fish oils and other oils of animal nature and their alkyl derivatives with and without surfactants, natural higher fatty acids, preferably having 8 to 28 carbon atoms, and their alkyl ester derivatives, organic acids which contain an aromatic ring system and one or more carboxylic esters, and their alkyl derivatives, furthermore suspensions of polymers of vinyl acetate or copolymers of vinyl acetate/acrylic esters. Mixtures of individual adjuvants with one another and in combination with organic solvents may further increase the effect.
Suitable nonionic surfactants are, for example, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, preferably those which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol preferably having 1 to 10 carbon atoms in the alkyl chain which preferably contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds generally contain 1 to 5 ethylene glycol units per propylene glycol unit.
Other examples of nonionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Also suitable are fatty esters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan trioleate.
Preferred anionic surfactants are, in particular, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylated phosphoric acids and their ethoxylated derivatives. The alkyl radicals usually contain 8 to 24 carbon atoms.
Preferred nonionic surfactants are known under the following trade names:
Polyoxyethylene cocoalkylamine (for example AMIET(copyright) 105 (Kao Co.)), polyoxyethylene oleylamine (for example AMIET(copyright) 415 (Kao Co.)), nonylphenolpolyethoxyethanols, polyoxyethylene stearylamine (for example AMIET(copyright) 320 (Kao Co.)), N-polyethoxyethylamines (for example GENAMIN(copyright) (Hoechst AG)), N,N,Nxe2x80x2,Nxe2x80x2-tetra(polyethoxypolypropoxyethyl)ethylene diamines (for example TERRONIL(copyright) and TETRONIC(copyright) (BASF Wyandotte Corp.)), BRIJ(copyright) (Atlas Chemicals), ETHYLAN(copyright) CD and ETHYLAN(copyright) D (Diamond Shamrock), GENAPOL(copyright) C, GENAPOL(copyright) O, GENAPOL(copyright) S and GENAPOL(copyright) X080 (Hoechst AG), EMULGEN(copyright) 104P, EMULGEN(copyright) 109P and EMULGEN(copyright) 408 (Kao Co.); DISTY(copyright) 125 (Geronazzo), SOPROPHOR(copyright) CY 18 (Rhxc3x4ne Poulenc S.A.); NONISOL(copyright) (Ciba-Geigy), MRYJ(copyright) (ICI); TWEEN(copyright) (ICI); EMULSOGEN(copyright) (Hoechst AG); AMIDOX(copyright) (Stephan Chemical Co.), ETHOMID(copyright) (Armak Co.); PLURONIC(copyright) (BASF Wyandotte Corp.), SOPROPHOR(copyright) 461P (Rhxc3x4ne Poulenc S.A.), SOPROPHOR(copyright) 496/P (Rhxc3x4ne Poulenc S.A.), ANTAROX FM-63 (Rhxc3x4ne Poulenc S.A.), SLYGARD 309 (Dow Coming), SILWET 408, SILWET L-7607N (Osi-Specialities).
The cationic surfactants are primarily quaternary ammonium salts which contain, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower nonhalogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The oils used are either of mineral or natural origin. The natural oils may additionally be of animal or vegetable origin. In the case of animal oils, preference is given, in particular, to derivatives of beef tallow, but fish oils (for example sardine oil) and derivatives thereof are also used. Vegetable oils are mainly seed oils of various origin. Examples of particularly preferred vegetable oils which may be mentioned are coconut, rapeseed or sunflower oils and derivatives thereof.
Surfactants, oils, in particular vegetable oils, derivatives thereof such as alkylated fatty acids and mixtures thereof, for example with preferably anionic surfactants such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulfonates and higher fatty acids which are customary in formulation and adjuvant technique and which can also be employed in the compositions according to the invention and spray tank solins thereof are described, inter alia, in xe2x80x9cMc Cutcheon""s Detergents and Emulsifiers Annualxe2x80x9d, MC Publishing Corp., Ridgewood N.J., 1998, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1990, M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol. I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, xe2x80x9cA Compendium of Herbicide Adjuvantsxe2x80x9d, Southern Illinois Univ., 1998, L. Thomson Harvey, xe2x80x9cA Guide to Agricultural Spray Adjuvants Used in the United Statesxe2x80x9d, Thomson Pubns., 1992.
The herbicidal formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant. While concentrated compositions are rather preferred as commercial goods, the end user as a rule uses dilute compositions. The compositions can also comprise further additives, such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active compounds.
The herbicidally active compounds of the formula I are as a rule applied to the plants or their habitat, at application rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dosage required for the desired effect can be determined by tests. It depends on the nature of the effect, the development stage of the crop plant and the weed and on the application (location, time, process) and can, as a function of these parameters, vary within wide ranges.
The compounds of the formula I have herbicidal and growth-inhibiting properties, owing to which they can be used in crops of useful plants, in particular in cereals, cotton, soya, sugar beet, sugar cane, plantings, rapeseed, maize and rice, very particularly in maize and cereals, and for the non-selective control of weeds. Crops include those which have been rendered tolerant towards herbicides or herbicide classes by conventional breeding methods or genetical engineering methods. The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Agrostis, Digitaria, Avena, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus, Alopecurus, Sorghum halepense, Sorghum bicolor, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, lpomoea, Chrysanthemum, Galium, Viola, Matricharia, Papaver and Veronica. The herbicidal composition according to the invention is particularly suitable for controlling Alopecurus, Avena, Agrostis, Setaria, Phalaris, Lolium, Panicum, Echinochloa, Brachiaria and Digitaria.
Surprisingly, it has been found that specific safeners known from U.S. Pat. Nos. 5,041,157, 5,541,148, 5,006,656, EP-A-0 094 349, EP-A-0 551 650, EP-A-0 268 554, EP-A-0 375 061, EP-A-0 174 562, EP-A-492 366, WO 91/7874, WO 94/987, DE-A-19 612 943, WO 96/29870, WO 98/13361, WO 98/39297, WO 98/27049, EP 716 073, EP 613 618, U.S. Pat. No. 5,597,776 and EP-A430 004 are suitable for mixing with the herbicidal composition according to the invention. Consequently, the present invention also relates to a selective herbicidal composition for controlling grasses and weeds in crops of useful plants, in particular in crops of maize and cereals, said composition comprising a herbicide of the formula I and a safener (antidote) and which protects the useful plants, but not the weeds, against the phytotoxic effect of the herbicide, and to the use of this composition for controlling weeds in crops of useful plants.
According to the invention, a selective-herbicidal composition is therefore proposed which, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, comprises, as active compound, a mixture of
a) a herbicidally effective amount of a compound of the formula I 
xe2x80x83in which
R1, R2, R3, R4, R5 and G are as defined above, and
b) a herbicide-antagonistically effective amount of either a compound of the formula X 
xe2x80x83in which
R37 is hydrogen, C1-C8alkyl or C1-C6alkoxy- or C3-C6alkenyloxy-substituted C1-C8alkyl; and X6 is hydrogen or chlorine; or a compound of the formula XI 
xe2x80x83in which
E is nitrogen or methine;
R38 is xe2x80x94CCl3, phenyl or halogen-substituted phenyl;
R39 and R40 independently of one another are hydrogen or halogen; and
R41 is C1-C4alkyl; or a compound of the formula XII 
xe2x80x83in which
R44 and R45 independently of one another are hydrogen or halogen and R46, R47 and R48 independently of one another are C1-C4alkyl, or a compound of the formula XIII 
xe2x80x83in which
A2 is a group 
R51 and R52 independently of one another are hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, 
xe2x80x83or C1-C4alkoxyxe2x80x94 or 
xe2x80x83substituted C1-C4alkyl; or R51 and R52 together form a C4-C6alkylene bridge which may be interrupted by oxygen, sulfur, SO, SO2, NH or xe2x80x94N(C1-C4alkyl)xe2x80x94,
R53 is hydrogen or C1-C4alkyl;
R49 is hydrogen, halogen, cyano, trifluoromethyl, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsullonyl, xe2x80x94COORj, xe2x80x94CONRkRm, xe2x80x94CORn, xe2x80x94SO2NRkRm or xe2x80x94OSO2xe2x80x94C1-C4alkyl;
Rg is hydrogen, halogen, cyano, nitro, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj, CONRkRm, xe2x80x94CORn, SO2NRkRm, xe2x80x94OSO2xe2x80x94C1-C4alkyl, C1-C6alkoxy, or C1-C6alkoxy which is substituted by C1-C4alkoxy or halogen, C3-C6alkenyloxy, or C3-C6alkenyloxy which is substituted by halogen, or C3-C6alkynyloxy, or R49 and R50 together form a C3-C4alkylene bridge which may be substituted by halogen or C1-C4alkyl, or they form a C3-C4alkenylene bridge which may be substituted by halogen or C1-C4alkyl, or they form a C4alkadienylene bridge which may be substituted by halogen or C1-C4alkyl;
R50 and Rh independently of one another are hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C6alkoxy, C1-C6alkylthio or xe2x80x94COORj;
Rc is hydrogen, halogen, nitro, C1-C4alkyl or methoxy; Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj or CONRkRm;
Re is hydrogen, halogen, C1-C4alkyl, xe2x80x94COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4alkylene bridge;
Rp is hydrogen, halogen, C1-C4alkyl, xe2x80x94COORj, trifluoromethyl or methoxy; Rq is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj or CONRkRm, or Rp and Rq together form a C3-C4alkylene bridge;
Rr is hydrogen, halogen, C1-C4alkyl, xe2x80x94COORj, trifluoromethyl or methoxy; Rs is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj or CONRkRm, or Rr and Rs together form a C3-C4alkylene bridge;
Rt is hydrogen, halogen, C1-C4alkyl, xe2x80x94COORj, trifluoromethyl or methoxy; Ru is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj or CONRkRm, or Rv and Ru together form a C3-C4alkylene bridge;
Rf and Rv are hydrogen, halogen or C1-C4alkyl; Rx and Ry independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, xe2x80x94COOR54, trifluoromethyl, nitro or cyano;
Rj, Rk and Rm independently of one another are hydrogen or C1-C4alkyl; or Rk and Rm together form a C4-C6alkylene bridge which may be interrupted by oxygen, NH or xe2x80x94N(C1-C4alkyl)xe2x80x94;
Rn is C1-C4alkyl, phenyl, or halogen-, C1-C4alkyl-, methoxy-, nitro or trifluoromethyl-substituted phenyl;
R54 is hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, halo-C1-C8alkyl, C2-C8alkenyl, halo-C2-C8alkenyl, C3-C8alkynyl, CC7cycloalkyl, halo-C3-C7cycloalkyl, C1-C8alkylcarbonyl, allylcarbonyl, C3-C7cycloalkylcarbonyl, benzoyl which is unsubstituted or substituted up to three times on the phenyl ring by identical or different substituents selected from the group consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy or C1-C4alkoxy; or furoyl, thienyl; or C1-C4alkyl which is substitute by phenyl, halophenyl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkylthiocarbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkynylthiocarbonyl, carbamoyl, mono-C1-C4alkylaminocarbonyl, di-C1-C4alkylaminocarbonyl; or phenylaminocarbonyl which is unsubstituted or substituted up to three times on the phenyl by identical or different substituents selected from the group consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy and C1-C4alkoxy, or is monosubstituted by cyano or nitro, or dioxoian-2-yl which is unsubstituted or substituted by one or two C1-C4alkyl radicals, or dioxan-2-yl which is unsubstituted or substituted by one or two C1-C4alkyl radicals, or C1-C4alkyl which is substituted by cyano, nitro, carboxyl or C1-C8alkylthio-C1-C8alkoxycarbonyl;
or a compound of the formula XIV 
xe2x80x83in which
R56 and R57 independently of one another are C1-C6alkyl or C2-C6alkenyl; or R56 and
R57 together are 
xe2x80x83R58 and R59 independently of one another are hydrogen or C1-C6alkyl; or R56 and R57 together are 
R60 and R61 independently of one another are C1-C4alkyl, or R60 and R61 together are xe2x80x94(CH2)5xe2x80x94;
R62 is hydrogen, C1-C4alkyl or 
xe2x80x83or R56 and R57 together are 
R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73, R74, R75, R76, R77 and R78 independently of one another are hydrogen or C1-C4alkyl;
or a compound of the formula XV 
xe2x80x83in which
R80 is hydrogen or chlorine and R79 is cyano or trifluoromethyl,
or a compound of the formula XVI 
xe2x80x83in which
R81 is hydrogen or methyl,
or of the formula XVII 
xe2x80x83in which
R82 is hydrogen, C1-C4alkyl, C1-C4alkyl which is substituted by C1-C4alkyl-X2xe2x80x94 or C1-C4haloalkyl-X2xe2x80x94, C1-C4haloalkyl, nitro, cyano, xe2x80x94COOR85, xe2x80x94NR86R87, xe2x80x94SO2NR88R89 or xe2x80x94CONR90R91;
R83 is hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C4alkoxy or C1-C4haloalkoxy;
R84 is hydrogen, halogen or C1-C4alkyl;
U, V, W, and Z4 independently of one another are oxygen, sulfur, C(R92)R93, carbonyl, NR94, 
xe2x80x83in which R102 is C2-C4alkenyl or C2-C4alkynyl; with the proviso that
a) at least one of the ring members U, V, W, or Z4 is carbonyl, and a ring member which is adjacent to this or these ring members is the group 
xe2x80x83this group being present only once; and
b) two adjacent ring members U and V, V and W1 and W1 and Z4 may not simultaneously be oxygen;
R95 and R96 independently of one another are hydrogen or C1-C8alkyl; or
R95 and R96 together form a C2-C6alkylene group;
A1 is R99xe2x80x94Y1xe2x80x94 or xe2x80x94NR97R98;
X2 is oxygen or xe2x80x94S(O)s;
Y1 is oxygen or sulfur;
R99 is hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-C4alkoxy-C1-C8alkyl, C3-C6alkenyloxy-C1-C8alkyl or phenyl-C1-C8alkyl, where the phenyl ring may be substituted by halogen, C1-C4alkyl, trifluoromethyl, methoxy or methyl-S(O)5xe2x80x94, C3-C6alkenyl, C3-C6haloalkenyl, phenyl-C3-C6alkenyl, C3-C6alkynyl, phenyl-C3-C6alkynyl, oxetanyl, furyl or tetrahydroturyl;
R85 is hydrogen or C1-C4alkyl;
R86 is hydrogen, C1-C4alkyl or C1-C4alkylcarbonyl;
R87 is hydrogen or C1-C4alkyl; or
R86 and R87 together form a C4- or C5alkylene group;
R88, R89, R90 and R91 independently of one another are hydrogen or C1-C4alkyl; or R88 together with R89 or R90 together with R91 independently of one another are C4- or C5-alkylene, where a carbon atom may be replaced by oxygen or sulfur, or one or two carbon atoms may be replaced by xe2x80x94NR100xe2x80x94;
R92, R100 and R93 independently of one another are hydrogen or C1-C8alkyl; or
R92 and R93 together are C2-C6alkylene;
R94 is hydrogen or C1-C8alkyl;
R97 is hydrogen, C1-C8alkyl, phenyl, phenyl-C1-C8alkyl, where the phenyl rings may be substituted by fluorine, chlorine, bromine, nitro, cyano, xe2x80x94OCH3, C1-C4alkyl or CH3SO2xe2x80x94, C1-C4alkoxy-C1-C8alkyl, C3-C6alkenyl or C3-C6alkynyl;
R98 is hydrogen, C1-C8alkyl, C3-C6alkenyl or C3-C6alkynyl; or
R97 and R98 together are C4- or C5-alkylene, where a carbon atom may be replaced by oxygen or sulfur, or one or two carbon atoms may be replaced by xe2x80x94NR101xe2x80x94;
R101 is hydrogen or C1-C4alkyl;
r is 0 or 1; and
s is 0, 1 or 2, or a compound of the formula XVIII 
xe2x80x83in which
R103 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl, C3-C6alkenyl or C3-C6alkynyl; and R104, R105 and R106 independently of one another are hydrogen, C1-C6alkyl, C3-C6cycloalkyl or C1-C6alkoxy, with the proviso that one of the substituents R104, R105 and R106 is different from hydrogen;
a compound of the formula XIX 
xe2x80x83in which
Z5 is N or CH, n, in the case where Z5 is N, is 0, 1, 2 or 3 and, in the case where Z5 is CH, is 0, 1, 2, 3 or 4, R107 is halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro, C1-C4alkylthio, C1-C4alkylsulfonyl, C1-C4alkoxycarbonyl or unsubstituted or substituted phenyl or phenoxy, R108 is hydrogen or C1-C4alkyl, R109 is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C4haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylsulfonyl-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkenyloxy-C1-C4alkyl or C1-C4alkynyloxy-C1-C4alkyl;
a compound of the formula XX 
xe2x80x83in which
Z6 is O or Nxe2x80x94R110 and R110 is a group of the formula 
xe2x80x83in which
R111 and R112 independently of one another are cyano, hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, unsubstituted or substituted phenyl or heteroaryl;
compound of the formula XXI 
xe2x80x83in which
Z7 is O, S, Sxe2x95x90O, SO2 or CH2, R113 and R114 independently of one another are hydrogen, halogen or C1-C4alkyl, W2 and W3 independently of one another are CH2COOR115, COOR115 or together are a group of the formula xe2x80x94(CH2)C(O)xe2x80x94Oxe2x80x94C(O)xe2x80x94(CH2)xe2x80x94, and R115 is hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C1-C4haloalkyl, a metal cation or an ammonium cation;
a compound of the formula XXII 
xe2x80x83in which
R119 and R120 independently of one another are hydrogen, halogen or C1-C4haloalkyl, R121 is hydrogen, C1-C4alkyl, C3-C4alkenyl, C3-C4alkynyl, C1-C4haloalkyl, C3-C6cycloalkyl, a metal cation or an ammonium cation, Z8 is N, CH, Cxe2x80x94F or Cxe2x80x94Cl and
W4 is a group of the formula 
xe2x80x83in which
R122 and R123 independently of one another are hydrogen or C1-C4alkyl and R124 and R125 independently of one another are hydrogen or C1-C4alkyl;
a compound of the formula XXIII 
xe2x80x83in which
R126 is hydrogen, cyano, halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkoxy, C1-C4alkoxycarbonyl, C1-C4alkylthiocarbonyl, xe2x80x94NHxe2x80x94R128, xe2x80x94C(O)NHxe2x80x94R128, unsubstituted or substituted aryl or heteroaryl,
R127 is hydrogen, cyano, nitro, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4thioalkyl, C1-C4haloalkyl, xe2x80x94NHxe2x80x94R128, xe2x80x94C(O)NHxe2x80x94R128, unsubstituted or substituted aryl, heteroaryl, and R128 is C1-C4alkyl, C1-C4haloalkyl, C3-C4alkenyl, C3-C4alkynyl, C3-C4cycloalkyl, unsubstituted or substituted aryl or heteroaryl, formyl, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl;
a compound of the formula XXIV 
xe2x80x83in which
R129 and R130 independently of one another are hydrogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, mono-C1-C8- or di-C1-C8alkylamino, C3-C6cycloalkyl, C1-C4thioalkyl, phenyl or heteroaryl, R131 has the meaning of R129 and is additionally OH, NH2, halogen, di-C1-C4aminoalkyl, C1-C4alkylthio, C1-C4alkylsulfonyl or C1-C4alkoxycarbonyl, R132 has the meaning of R129 and is additionally cyano, nitro, carboxyl, C1-C4alkoxycarbonyl, di-C1-C4aminoalkyl, C1-C4alkylthio, C1-C4alkylsulfonyl, SO2xe2x80x94OH, iso-C1-C4aminoalkylsulfonyl or C1-C4alkoxysulfonyl, R133 has the meaning of R129 and is additionally OH, NH2, halogen, di-C1-C4aminoalkyl, pyrrolidin-1-yl, piperidin-1-yl, morpholin-1-yl, C1-C4alkylthio, C1-C4alkylsulfonyl, C1-C4alkoxycarbonyl, phenoxy, naphtoxy, phenylamino, benzoyloxy or phenylsulfonyloxy;
or a compound of the formula XXV 
xe2x80x83in which
R134 is hydrogen, C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl or C1-C4alkoxy-C1-C4alkyl, R135 is hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy and R136 is hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, with the proviso that R135 and R136 are not simultaneously hydrogen.
The selective-herbicidal composition according to the invention preferably comprises, as herbicide-antagonistically effective amount, either a compound of the formula X 
in which
R37 is hydrogen, C1-C6alkyl or C1-C6alkoxy- or C3-C6alkenyloxy-substituted C1-C8alkyl; and X6 is hydrogen or chlorine; or a compound of the formula XI 
in which
E is nitrogen or methine; R38 is xe2x80x94CCl3, phenyl or halogen-substituted phenyl;
R39 and R40 independently of one another are hydrogen or halogen; and
R41 is C1-C4alkyl; or a compound of the formula XII 
in which
R44 and R45 independently of one another are hydrogen or halogen and R46, R47 and R48 independently of one another are C1-C4alkyl.
The abovementioned preferences for the compounds of the formula I also apply to mixtures of the compounds of the formula I with safeners of the formulae X to XVIII. Preferred compositions according to the invention comprise a safener selected from the group consisting of the formula Xa 
the formula Xb 
and the formula XIa 
Other preferred compounds of the formulae X, XI and XII are also listed in Tables 9, 10 and 11.
Preferred compounds of the formula XI are listed in Table 10 below.
Preferred compounds of the formula XII are listed in Table 11 below.
Preferred compounds of the formula XII are listed in Table 12 below as compounds of the formula XIIIa:
Preferred compounds of the formula XIV are listed in Table 13 below:
Preferred compounds of the formula XV are listed in Table 14 below:
Preferred compounds of the formula XVI are listed in Table 15 below:
Preferred compounds of the formula XVII are listed in Table 16 below as compounds of the formula XVIIa:
Preferred compounds of the formula XVII are listed in Table 17 below as compounds of the formula XVIIb:
Preferred compounds of the formula XVII are listed in Table 18 below as compounds of the formula XVIIc:
Preferred compounds of the formula XVII are listed in Table 19 below as compounds of the formula XVIId:
Preferred compounds of the formula XVIII are listed in Table 20 below:
The invention also relates to a method for the selective control of weeds in crops of useful plants which comprises treating the useful plants, their seeds or seedlings or the area on which they are cultivated jointly or separately with a herbicidally effective amount of the herbicide of the formula I and a herbicide-antagonistically effective amount of the safener of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII.
Crop plants which can be protected against the damaging effect of the abovementioned herbicides by the safeners of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII are, in particular, cereals, cotton, soya, sugarbeet, sugarcane, plantings, rapeseed, maize and rice, very particularly maize and cereals. Crops are to be understood as including those which have been rendered tolerant towards herbicides or classes of herbicides by conventional breeding methods or genetical engineering methods.
The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds, for example the monocotyledonous weeds Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitaria Brachiaria, Echinochloa, Panicum, Sorghum hal./bic., Rottboellia, Cyperus, Brachiaria, Scirpus, Monochoria, Sagittaria, and Stellaria and the dicotyledonous weeds Sinapis, Chenopodium, Galium, Viola, Veronica, Matricaria, Papaver, Solanum, Abutilon, Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum.
Areas under cultivation are the areas on which the crop plants are already growing, or on which the seeds of these crop plants have been sown, and also the soils which are intended to be cultivated with these crop plants.
Depending on the intended use, a safener of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII can be employed for pretreating the seeds of the crop plant (dressing of the seeds or the seedlings), or it can be worked into the soil before or after seeding. However, it can also be applied on its own or together with the herbicide after the plants have emerged. Thus, the treatment of the plants or the seeds with the safener can, in principle, be carried out independently of when the herbicide is applied. However, the plant can also be treated by simultaneous application of herbicide and safener (for example as tank mix). The application rate of safener to herbicide to be applied depends essentially on the type of application. In a field treatment which is carried out either by using a tank mix of a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicide to safener is as a rule from 100:1 to 1:10, preferably from 20:1 to 1:1. As a rule, 0.001 to 1.0 kg of safener/ha, preferably 0.001 to 0.25 kg of safener/ha are applied in the field treatment.
The application rates of herbicide are as a rule between 0.001 and 2 kg/ha, but preferably between 0.005 to 0.5 kg/ha.
The compositions according to the invention are suitable for all application methods which are customary in agriculture, for example preemergence application, postemergence application and seed dressing.
For seed dressing, generally 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form while swelling the seeds shortly before seeding, it is advantageous to employ safener solutions which comprise the active compound in a concentration of from 1 to 10000, preferably from 100 to 1000, ppm.
For application, the safeners of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII or combinations of these safeners with the herbicides of the formula I are advantageously processed together with auxiliaries conventionally used in the art of formulation, for example to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The formulations are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with liquid or solid formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) can furthermore additionally be used during preparation of the formulations. Solvents and solid carriers which are suitable for this purpose are mentioned, for example, in WO 97/34485 on page 6.
Suitable surface-active compounds are, depending on the nature of the active compound of the formula I to be formulated, nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, nonionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8. The surfactants conventionally used in the art of formulation and which can also be used in the preparation of the herbicidal compositions according to the invention are described, inter alia, in xe2x80x9cMc Cutcheon""s Detergents and Emulsifiers Annualxe2x80x9d, MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol I-III, Chemical Publishing Co., New York, 1980-81.
The herbicidal formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the active compound mixture of the compound of the formula I with the compounds of the formulae X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII, 1 to 99.9% by weight of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant. While concentrated compositions are usually preferred as commercial goods, the end user as a rule uses dilute compositions.
The compositions can also comprise further additives, such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active substances. For using safeners of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII or compositions comprising them to protect crop plants against damaging effects of herbicides of the formula I, various methods and techniques are suitable, for example the following:
i) Seed Dressing
a) Dressing the seeds with an active compound of the formula X, XI, XII, XII, XIV, XV, XVI, XVII or XVIII formulated as a wettable powder by shaking in a vessel until even distribution on the surface of the seeds is achieved (dry dressing). Here, approximately 1 to 500 g of active compound of the formula X, XI, XII, XII, XIV, XV, XVI, XVII or XVIII (4 g to 2 kg of wettable powder) are employed per 100 kg of seed.
b) Dressing the seeds using an emulsion concentrate of the active compound of the formula X, XI, XII, XII, XIV, XV, XVI, XVII or XVIII according to method a) (wet dressing).
c) Dressing by dipping the seeds for 1 to 72 hours into a liquor containing 1-1000 ppm of active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII, with or without subsequent drying of the seeds (dip dressing).
Seed dressing or the treatment of the germinated seedling are the naturally preferred application methods, since the treatment with active compound is completely directed at the target culture. As a rule, 1 to 1000 g of antidote, preferably 5 to 250 g of antidote, are employed per 100 kg of seed, but, depending on the method, which also permits the addition of other active compounds or micronutrients, it is possible to deviate above or below the stated limit concentrations (repeat dressing).
ii) Application as Tank Mix
A liquid preparation of a mixture of antidote and herbicide (mutual ratio between 10:1 and 1:100) is employed, the application rate of herbicide being from 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after seeding.
iii) Application in the Seed Farrow
The active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII is applied into the open seeded seed farrow as an emulsion concentrate, a wettable powder or as granules. After the seed farrow has been covered, the herbicide is applied in a customary manner by the pre-emergence method.
iv) Controlled Release of Active Compound
The active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII is absorbed in solution onto mineral granule carriers or polymerized granules (urea/formaldehyde) and dried. If appropriate, a coating which allows the active compound to be released in metered form over a certain period of time can be applied (coated granules).
The efficacy of herbicidal and plant-growth-inhibiting compositions according to the invention comprising a herbicidally effective amount of a compound of the formula I and a herbicide-antagonistically effective amount of a compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII can be increased by addition of spray tank adjuvants. These adjuvants may be, for example, nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with or without surfactants, vegetable oil derivatives with or without addition of surfactants, alkylated derivatives of oils of vegetable or mineral origin with or without surfactants, fish oils and other oils of animal nature and their alkyl derivatives with or without surfactants, natural higher fatty acids, preferably having 8 to 28 carbon atoms, and their alkyl ester derivatives, organic acids which contain an aromatic ring system and one or more carboxylic esters, and their alkyl derivatives, furthermore suspensions of polymers of vinyl acetate or copolymers of vinyl acetate/acrylic esters. Mixtures of individual adjuvants with one another and in combination with organic solvents may further increase the effect.
Suitable nonionic surfactants are, for example, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, preferably those which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol preferably having 1 to 10 carbon atoms in the alkyl chain which preferably contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds generally contain 1 to 5 ethylene glycol units per propylene glycol unit.
Other examples of nonionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Also suitable are fatty esters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan trioleate.
Preferred anionic surfactants are, in particular, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylated phosphoric acids and their ethoxylated derivatives. The alkyl radicals usually contain 8 to 24 carbon atoms.
Preferred nonionic surfactants are known under the following trade names:
Polyoxyethylene cocoalkylamine (for example AMIET(copyright) 105 (Kao Co.)), polyoxyethylene oleylamine (for example AMIET(copyright) 415 (Kao Co.)), nonylphenolpolyethoxyethanols, polyoxyethylene stearylamine (for example AMIET(copyright) 320 (Kao Co.)), N-polyethoxyethylamines (for example GENAMIN(copyright) (Hoechst AG)), N,N,Nxe2x80x2,Nxe2x80x2-tetra(polyethoxypolypropoxyethyl)ethylene diamines (for example TERRONIL(copyright) and TETRONIC(copyright) (BASF Wyandotte Corp.)), BRIJ(copyright) (Atlas Chemicals), ETHYLAN(copyright) CD and ETHYLAN(copyright) D (Diamond Shamrock), GENAPOL(copyright) C, GENAPOL(copyright) O, GENAPOL(copyright) S and GENAPOL(copyright) X080 (Hoechst AG), EMULGEN(copyright) 104P, EMULGEN(copyright) 109P and EMULGEN(copyright) 408 (Kao Co.); DISTY(copyright) 125 (Geronazzo), SOPROPHOR(copyright) CY 18 (Rhxc3x4ne Poulenc S.A.); NONISOL(copyright) (Ciba-Geigy), MRYJ(copyright) (ICI); TWEEN(copyright) (ICI); EMULSOGEN(copyright) (Hoechst AG); AMIDOX(copyright) (Stephan Chemical Co.), ETHOMID(copyright) (Armak Co.); PLURONIC(copyright) (BASF Wyandotte Corp.), SOPROPHOR(copyright) 461P (Rhxc3x4ne Poulenc S.A.), SOPROPHOR(copyright) 496/P (Rhxc3x4ne Poulenc S.A.), ANTAROX FM-63 (Rhxc3x4ne Poulenc S.A.), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N (Osi-Specialities).
The cationic surfactants are primarily quaternary ammonium salts which contain, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower nonhalogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The oils used are either of mineral or natural origin. The natural oils may additionally be of animal or vegetable origin. In the case of animal oils, preference is given, in particular, to derivatives of beef tallow, but fish oils (for example sardine oil) and derivatives thereof are also used. Vegetable oils are mainly seed oils of various origin. Examples of particularly preferred vegetable oils which may be mentioned are coconut, rapeseed or sunflower oils and derivatives thereof.
Surfactants, oils, in particular vegetable oils, derivatives thereof such as alkylated fatty acids and mixtures thereof, for example with preferably anionic surfactants such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulfonates and higher fatty acids which are customary in formulation and adjuvant technique and which can also be employed in the compositions according to the invention and spray tank solutions thereof are described, inter alia, in xe2x80x9cMc Cutcheon""s Detergents and Emulsifiers Annualxe2x80x9d, MC Publishing Corp., Ridgewood N.J., 1998, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1990, M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol. I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, xe2x80x9cA Compendium of Herbicide Adjuvantsxe2x80x9d, Southern Illinois Univ., 1998, L. Thomson Harvey, xe2x80x9cA Guide to Agricultural Spray Adjuvants Used in the United Statesxe2x80x9d, Thomson Pubns., 1992.
In particular, preferred formulations have the following compositions:
(%=per cent by weight)